An oled device having two spaced electrodes including: first, second, and third light-emitting units disposed between the electrodes, the first light-emitting unit produces light that has multiple peaks at wavelengths longer than 500 nm and substantially no emission at wavelengths shorter than 480 nm, and the second and third light-emitting units produce light that has substantial emission at wavelengths shorter than 500 nm; intermediate connectors respectively disposed between the first and second light-emitting units, and between the second and third light-emitting units; and wherein the oled device emits light with a color temperature greater than 7,000K.
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1. An oled device having two spaced electrodes comprising:
a. first, second, and third light-emitting units disposed between the electrodes, the first light-emitting unit produces light that has multiple peaks at wavelengths longer than 500 nm and substantially no emission at wavelengths shorter than 480 nm, and the second and third light-emitting units produce light that has substantial emission at wavelengths shorter than 500 nm;
b. intermediate connectors respectively disposed between the first and second light-emitting units, and between the second and third light-emitting units; and
c. wherein the oled device emits light with a color temperature greater than 7,000K.
2. The oled device of
3. The oled device of
4. The oled device of
5. The oled device of
6. The oled device of
7. The oled device of
8. The oled device of
9. The oled device of
10. The oled device of
11. The oled device of
12. The oled device of
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Reference is made to commonly assigned U.S. Pat. No. 7,332,860, entitled EFFICIENT WHITE-LIGHT OLED DISPLAY WITH FILTERS by Hatwar et al.; U.S. patent application Ser. No. 11/749,883, entitled HYBRID OLED WITH FLUORESCENT AND PHOSPHORESCENT LAYERS by Deaton et al.; and U.S. patent application Ser. No. 11/749,899, entitled HYBRID FLUORESCENT/PHOSPHORESCENT OLEDS by Deaton et al.; the disclosures of which are incorporated herein by reference.
The present invention relates to broadband light-producing OLED displays suitable for large displays.
An organic light-emitting diode device, also called an OLED, commonly includes an anode, a cathode, and an organic electroluminescent (EL) unit sandwiched between the anode and the cathode. The organic EL unit includes at least a hole-transporting layer (HTL), a light-emitting layer (LEL), and an electron-transporting layer (ETL). OLEDs are attractive because of their low drive voltage, high luminance, wide viewing-angle, and capability for full color displays and for other applications. Tang et al. described this multilayer OLED in their U.S. Pat. Nos. 4,769,292 and 4,885,211.
OLEDs can emit different colors, such as red, green, blue, or white, depending on the emitting property of its LEL. Recently, there is an increasing demand for broadband OLEDs to be incorporated into various applications, such as a solid-state lighting source, color display, or a full color display. By broadband emission, it is meant that an OLED emits sufficiently broad light throughout the visible spectrum so that such light can be used in conjunction with filters or color change modules to produce displays with at least two different colors or a full color display. In particular, there is a need for broadband-light-emitting OLEDs (or broadband OLEDs) where there is substantial emission in the red, green, and blue portions of the spectrum, i.e., a white-light-emitting OLED (white OLED). The use of white OLEDs with color filters provides a simpler manufacturing process than an OLED having separately patterned red, green, and blue emitters. This can result in higher throughput, increased yield, and cost savings. White OLEDs have been reported, e.g. by Kido et al. in Applied Physics Letters, 64, 815 (1994), J. Shi et al. in U.S. Pat. No. 5,683,823, Sato et al. in JP 07-142169, Deshpande et al. in Applied Physics Letters, 75, 888 (1999), and Tokito, et al. in Applied Physics Letters, 83, 2459 (2003).
In order to achieve broadband emission from an OLED, more than one type of molecule has to be excited, because each type of molecule only emits light with a relatively narrow spectrum under normal conditions. A light-emitting layer having a host material and one or more luminescent dopant(s) can achieve light emission from both the host and the dopant(s) resulting in a broadband emission in the visible spectrum if the energy transfer from the host material to the dopant(s) is incomplete. To achieve a white OLED having a single light-emitting layer, the concentrations of light-emitting dopants must be carefully controlled. This produces manufacturing difficulties. A white OLED having two or more light-emitting layers can have better color and better luminance efficiency than a device with one light-emitting layer, and the variability tolerance for dopant concentration is higher. It has also been found that white OLEDs having two light-emitting layers are typically more stable than OLEDs having a single light-emitting layer. However, it is difficult to achieve light emission with strong intensity in the red, green, and blue portions of the spectrum. A white OLED with two light-emitting layers typically has two intensive emission peaks.
A tandem OLED structure (sometimes called a stacked OLED or a cascaded OLED) has been disclosed by Jones et al. in U.S. Pat. No. 6,337,492, Tanaka et al. in U.S. Pat. No. 6,107,734, Kido et al. in JP Patent Publication 2003/045676A and U.S. Patent Publication 2003/0189401 A1, and Liao et al. in U.S. Pat. No. 6,717,358 and U.S. Patent Publication 2003/0170491 A1. This tandem OLED is fabricated by stacking several individual OLED units vertically and driving the stack using a single power source. The advantage is that luminance efficiency, lifetime, or both are increased. However, the tandem structure increases the driving voltage approximately in proportion to the number of OLED units stacked together.
Matsumoto and Kido et al. reported in SID 03 Digest, 979 (2003) that a tandem white OLED is constructed by connecting a greenish blue EL unit and an orange EL unit in the device, and white light emission is achieved by driving this device with a single power source. Although luminance efficiency is increased, this tandem white OLED device has weaker green and red color components in the spectrum. In U.S. Patent Publication 2003/0170491 A1, Liao et al. describe a tandem white OLED structure by connecting a red EL unit, a green EL unit, and a blue EL unit in series within the device. When the tandem white OLED is driven by a single power source, white light emission is formed by spectral combination from the red, green, and blue EL units.
Notwithstanding these developments, there remains a need to improve efficiency and luminance stability of OLED devices while maintaining good broadband emission. Further, much work has been done to produce OLED displays having a broadband emission near the color of CIE Standard Illuminant D65, which has a color temperature of approximately 6500K. Many commercially available liquid-crystal and plasma displays are set with a color temperature of 9300K or above, which is a much bluer white. Thus, there is also a need to produce efficient and stable OLED displays with a higher color temperature.
There is a need for OLED devices with improved color temperature, efficiency, and luminance stability.
This object is achieved by an OLED device having two spaced electrodes comprising:
a. first, second, and third light-emitting units disposed between the electrodes, the first light-emitting unit produces light that has multiple peaks at wavelengths longer than 500 nm and substantially no emission at wavelengths shorter than 480 nm, and the second and third light-emitting units produce light that has substantial emission at wavelengths shorter than 500 nm;
b. intermediate connectors respectively disposed between the first and second light-emitting units, and between the second and third light-emitting units; and
c. wherein the OLED device emits light with a color temperature greater than 7,000K.
It is an advantage of this invention that it provides an OLED display with an improved color temperature for larger displays and with improved efficiency and lifetime.
Since device feature dimensions such as layer thicknesses are frequently in sub-micrometer ranges, the drawings are scaled for ease of visualization rather than dimensional accuracy.
The term “OLED device” is used in its art-recognized meaning of a display device comprising organic light-emitting diodes as pixels. It can mean a device having a single pixel. The terms “tandem OLED device” and “stacked OLED device” mean an OLED device comprising two or more light-emitting units arranged vertically, wherein each light-emitting unit is capable of light-emission independently of the others. Each light-emitting unit includes at least a hole-transporting layer, a light-emitting layer, and an electron-transporting layer. The light-emitting units are separated by intermediate connectors. The term “OLED display” as used herein means an OLED device comprising a plurality of pixels, which can be of different colors. A color OLED device emits light of at least one color. The term “multicolor” is employed to describe a display panel that is capable of emitting light of a different hue in different areas. In particular, it is employed to describe a display panel that is capable of displaying images of different colors. These areas are not necessarily contiguous. The term “full color” is employed to describe multicolor display panels that are capable of emitting in the red, green, and blue regions of the visible spectrum and displaying images in any combination of hues. The red, green, and blue colors constitute the three primary colors from which all other colors can be generated by appropriate mixing. The term “hue” refers to the intensity profile of light emission within the visible spectrum, with different hues exhibiting visually discernible differences in color. The term “pixel” is employed in its art-recognized usage to designate an area of a display panel that is stimulated to emit light independently of other areas. It is recognized that in full color systems, several pixels of different colors will be used together to produce a wide range of colors, and a viewer can term such a group a single pixel. For the purposes of this discussion, such a group will be considered several different colored pixels.
In accordance with this disclosure, broadband emission is light that has significant components in multiple portions of the visible spectrum, for example, blue and green. Broadband emission can also include the situation where light is emitted in the red, green, and blue portions of the spectrum in order to produce white light. White light is that light that is perceived by a user as having a white color, or light that has an emission spectrum sufficient to be used in combination with color filters to produce a practical full color display. For low power consumption, it is often advantageous for the chromaticity of the white-light-emitting OLED to be close to CIE Standard Illuminant D65, i.e. 1931 CIE chromaticity coordinates of CIEx=0.31 and CIEy=0.33. This is particularly the case for so-called RGBW displays having red, green, blue, and white pixels. Although CIEx, CIEy coordinates of about 0.31, 0.33 are ideal in some circumstances, the actual coordinates can vary significantly and still be very useful. For some applications, such as televisions and other large displays, it can be desirable to have a white emission with a higher color temperature, which means a more blue emission than D65. Color temperature is the equivalent temperature of a light source of a heated subject called a “black body” and is expressed on an absolute temperature scale in degrees Kelvin. Furthermore, the correlated color temperature, or CCT, is defined as the value of the temperature of the black body radiator when the radiator color matches that of the light source, but does not imply a spectral match. (A. R. Robertson, “Computation of Correlated Color Temperature and Distribution Temperature,” J. Opt. Soc. Am. 58, 1528-1535 (1968)). The term “color temperature” as used in this application actually refers to the correlated color temperature. As the white emission becomes bluer, the color temperature increases. For such displays, a desirable white emission can have CIE coordinates of 0.25 to 0.30 for both CIEx and CIEy. Preferably, the white emission would have CIE coordinates of x=0.28 and y=0.29, corresponding to a color temperature of 10,000K. One method of producing a bluer white is to increase the average intensity of the blue pixels of the display. However, this would have the deleterious effect of reducing the lifetimes of the blue pixels. The term “white-light-emitting” as used herein refers to a device that produces white light internally, even though part of such light can be removed by color filters before viewing.
Turning now to
Tandem OLED device 10 further includes intermediate connectors disposed between the light-emitting units, e.g. intermediate connector 96 disposed between first and second light-emitting units 85 and 80, and intermediate connector 95 disposed between second and third light-emitting units 80 and 75. The intermediate connectors provide effective carrier injection into the adjacent EL units. Metals, metal compounds, or other inorganic compounds are effective for carrier injection. However, such materials often have low resistivity, which can result in pixel crosstalk. Also, the optical transparency of the layers constituting the intermediate connectors should be as high as possible to permit for radiation produced in the EL units to exit the device. Therefore, it is often preferred to use mainly organic materials in the intermediate connectors. Intermediate connectors and materials used in their construction have been described in detail by Hatwar et al. in US Publication 2007/0001587. Some further nonlimiting examples of intermediate connectors are described in U.S. Pat. Nos. 6,717,358 and 6,872,472, and U.S. Patent Publication 2004/0227460 A1.
An OLED device of this construction emits light with a higher color temperature than many prior art devices. An OLED device can be constructed in this way such that the device emits light with a color temperature greater than 7,000K, and usefully with a color temperature between 9,000K and 15,000K. This is a bluer white than the D65 point and is suitable and even desirable for larger displays, such as large-screen televisions.
Turning now to
Light-emitting layers such as those described herein produce light in response to hole-electron recombination. Desired organic light-emitting materials can be deposited by any suitable process such as evaporation, sputtering, chemical vapor deposition, electrochemical deposition, or radiation thermal transfer from a donor material. Useful organic light-emitting materials are well known. As more fully described in U.S. Pat. Nos. 4,769,292 and 5,935,721, the light-emitting layers of the OLED device comprise a luminescent or fluorescent material where electroluminescence is produced as a result of electron-hole pair recombination in this region. The light-emitting layers can be comprised of a single material, but more commonly include a host material doped with a guest compound or dopant where light emission comes primarily from the dopant. The dopant is selected to produce color light having a particular spectrum. The host materials in the light-emitting layers can be an electron-transporting material, a hole-transporting material, or another material that supports hole-electron recombination. The dopant is often chosen from highly fluorescent dyes that are generally singlet light-emitting compounds, that is, they emit light from an excited singlet state. However, phosphorescent compounds that are generally triplet light-emitting compounds, that is, they emit light from an excited triplet state, e.g., transition metal complexes as described in WO 98/55561, WO 00/18851, WO 00/57676, and WO 00/70655, are also useful. Dopants are typically coated as 0.01 to 10% by weight into the host material. Host and emitting molecules known to be of use include, but are not limited to, those disclosed in U.S. Pat. Nos. 4,768,292; 5,141,671; 5,150,006; 5,151,629; 5,294,870; 5,405,709; 5,484,922; 5,593,788; 5,645,948; 5,683,823; 5,755,999; 5,928,802; 5,935,720; 5,935,721; and 6,020,078. Blue light-emitting layer 50b and 51b comprise a host material and a blue-light-emitting dopant. The blue-light-emitting dopant can be a singlet or a triplet light-emitting compound. The light-emitting layers of first light-emitting unit 85, e.g. light-emitting layers 52g and 52y, can include as dopants singlet light-emitting compounds or triplet light-emitting compounds.
Metal complexes of 8-hydroxyquinoline and similar derivatives (Formula A) constitute one class of useful electron-transporting host materials capable of supporting electroluminescence, and are particularly suitable for light emission of wavelengths longer than 500 nm, e.g., green, yellow, orange, and red.
##STR00001##
wherein:
Z completes a heterocyclic nucleus containing at least two fused aromatic rings, at least one of which is an azole or azine ring. Additional rings, including both aliphatic and aromatic rings, can be fused with the two required rings, if required. To avoid adding molecular bulk without improving on function the number of ring atoms is usually maintained at 18 or less.
Benzazole derivatives constitute another class of useful host materials capable of supporting electroluminescence, and are particularly suitable for light emission of wavelengths longer than 400 nm, e.g., blue, green, yellow, orange or red. An example of a useful benzazole is 2,2′,2″-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole].
The host material in one or more of the light-emitting layers of the present invention can include an anthracene derivative having hydrocarbon or substituted hydrocarbon substituents at the 9 and 10 positions. For example, certain derivatives of 9,10-diarylanthracenes (Formula B) are known to constitute a class of useful host materials capable of supporting electroluminescence, and are particularly suitable for light emission of wavelengths longer than 400 nm, e.g., blue, green, yellow, orange or red
##STR00002##
wherein R1, R2, R3, and R4 represent one or more substituents on each ring where each substituent is individually selected from the following groups:
Group 4: heteroaryl or substituted heteroaryl of from 5 to 24 carbon atoms as necessary to complete a fused heteroaromatic ring of furyl, thienyl, pyridyl, quinolinyl or other heterocyclic systems;
Particularly useful are compounds wherein R1 and R2 represent additional aromatic rings. Specific examples of useful anthracene materials for use as a host in a light-emitting layer include:
##STR00003## ##STR00004## ##STR00005##
Hole-transporting materials useful as hosts in light-emitting layers are well known to include compounds such as an aromatic tertiary amine, where the latter is understood to be a compound containing at least one trivalent nitrogen atom that is bonded only to carbon atoms, at least one of which is a member of an aromatic ring. In one form the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine. Exemplary monomeric triarylamines are illustrated by Klupfel et al. in U.S. Pat. No. 3,180,730. Other suitable triarylamines substituted with one or more vinyl radicals or comprising at least one active hydrogen-containing group are disclosed by Brantley et al. in U.S. Pat. Nos. 3,567,450 and 3,658,520.
A more preferred class of aromatic tertiary amines are those which include at least two aromatic tertiary amine moieties as described in U.S. Pat. Nos. 4,720,432 and 5,061,569. Such compounds include those represented by structural Formula C.
##STR00006##
wherein:
In one embodiment, at least one of Q1 or Q2 contains a polycyclic fused ring structure, e.g., a naphthalene. When G is an aryl group, it is conveniently a phenylene, biphenylene, or naphthalene moiety.
A useful class of triarylamines satisfying structural Formula C and containing two triarylamine moieties is represented by structural Formula D.
##STR00007##
where:
##STR00008##
wherein R5 and R6 are independently selected aryl groups. In one embodiment, at least one of R5 or R6 contains a polycyclic fused ring structure, e.g., a naphthalene.
Another class of aromatic tertiary amines are the tetraaryldiamines. Desirable tetraaryldiamines include two diarylamino groups, such as indicated by Formula E, linked through an arylene group. Useful tetraaryldiamines include those represented by Formula F.
##STR00009##
wherein:
In a typical embodiment, at least one of Ar, R7, R8, and R9 is a polycyclic fused ring structure, e.g., a naphthalene.
The various alkyl, alkylene, aryl, and arylene moieties of the foregoing structural Formulae C, D, E, and F can each in turn be substituted. Typical substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and halogens such as fluoride, chloride, and bromide. The various alkyl and alkylene moieties typically contain from 1 to about 6 carbon atoms. The cycloalkyl moieties can contain from 3 to about 10 carbon atoms, but typically contain live, six, or seven carbon atoms—e.g., cyclopentyl, cyclohexyl, and cycloheptyl ring structures. The aryl and arylene moieties are usually phenyl and phenylene moieties.
In addition to a host material as described above, green light-emitting layer 52g also includes a green light-emitting dopant. A singlet green light-emitting dopant can include a quinacridone compound, e.g. a compound of the following structure:
##STR00010##
wherein substituent groups R1 and R2 are independently alkyl, alkoxyl, aryl, or heteroaryl; and substituent groups R3 through R12 are independently hydrogen, alkyl, alkoxyl, halogen, aryl, or heteroaryl, and adjacent substituent groups R3 through R10 can optionally be connected to form one or more ring systems, including fused aromatic and fused heteroaromatic rings, provided that the substituents are selected to provide an emission maximum between 510 nm and 540 nm. Alkyl, alkoxyl, aryl, heteroaryl, fused aromatic ring and fused heteroaromatic ring substituent groups can be further substituted. Some examples of useful quinacridones include those disclosed in U.S. Pat. No. 5,593,788 and in US2004/0001969A 1.
Examples of useful quinacridone green dopants include:
##STR00011##
A singlet green light-emitting dopant can also include a 2,6-diaminoanthracene light-emitting dopant, as represented by the formula below:
##STR00012##
wherein d1, d3-d5, and d7-d10 can be the same or different and each represents hydrogen or an independently selected substituent, and each h can be the same or different and each represents one or more independently selected substituents, provided that two substituents can combine to form a ring group and a-d are independently 0-5.
Green light-emitting layer 52g can optionally include a small amount of a blue light-emitting compound as a stabilizer. The presence of a blue light-emitting compound, which is a higher-energy dopant, provides greater luminance stability to the green emission of 2,6-diaminoanthracene dopants, while maintaining good efficiency of the green light-emitting dopants. Blue light-emitting compounds can be those described below for blue light-emitting layers 50b and 51b.
A singlet red-light-emitting compound can be used in yellow light-emitting layer 52y and can include a diindenoperylene compound of the following structure J:
##STR00013##
wherein:
Illustrative examples of useful red dopants of this class are shown by Hatwar et al. in U.S. Pat. No. 7,247,394, the contents of which are incorporated by reference.
Other singlet red dopants useful in the present invention belong to the DCM class of dyes represented by Formula K:
##STR00014##
wherein Y1-Y5 represent one or more groups independently selected from: hydro, alkyl, substituted alkyl, aryl, or substituted aryl; Y1-Y5 independently include acyclic groups or can be joined pairwise to form one or more fused rings; provided that Y3 and Y5 do not together form a fused ring.
In a useful and convenient embodiment that provides red luminescence, Y1-Y5 of Formula K are selected independently from: hydro, alkyl, and aryl. Structures of particularly useful dopants of the DCM class are shown by Ricks et al. in U.S. Pat. No. 7,252,893, the contents of which are incorporated by reference.
A singlet light-emitting yellow compound such as used in yellow light-emitting layer 52y can include a compound of the following structures:
##STR00015##
wherein A1-A6 and A1-A16 represent one or more substituents on each ring and where each substituent is individually selected from one of the following:
Examples of particularly useful yellow dopants are shown by Ricks et al.
Another class of useful singlet yellow dopants are described in U.S. Pat. No. 6,818,327 and are according to formula L3:
##STR00016##
wherein A″1-A″4 represent one or more substituents on each ring and where each substituent is individually selected from one of the following:
Particularly useful examples are where A″1 and A″3 are hydrogen and A″2 and A″4 are chosen from category 5.
A blue-light-emitting dopant that can be used in blue light-emitting layers 50b and 51b can include a bis(azinyl)azene boron complex compound of the structure M:
##STR00017##
wherein:
Some examples of the above class of dopants are disclosed by Ricks et al.,
Another class of singlet blue dopants is the perylene class. Particularly useful blue dopants of the perylene class include perylene and tetra-t-butylperylene (TBP).
Another particularly useful class of singlet blue dopants in this invention includes blue-emitting derivatives of such styrylarenes and distyrylarenes as distyrylbenzene, styrylbiphenyl, and distyrylbiphenyl, including compounds described in U.S. Pat. No. 5,121,029, and US Publication 2006/0093856 by Helber et al. Among such derivatives that provide blue luminescence, particularly useful are those substituted with diarylamino groups. Examples include bis[2-[4-[N,N-diarylamino]phenyl]vinyl]-benzenes of the general structure N1 shown below:
##STR00018##
[N,N-diarylamino][2-[4-[N,N-diarylamino]phenyl]vinyl]biphenyls of the general structure N2 shown below:
##STR00019##
and bis[2-[4-[N,N-diarylamino]phenyl]vinyl]biphenyls of the general structure N3 shown below:
##STR00020##
In Formulas N1 to N3, X1-X4 can be the same or different, and individually represent one or more substituents such as alkyl, aryl, fused aryl, halo, or cyano. In a preferred embodiment, X1-X4 are individually alkyl groups, each containing from one to about ten carbon atoms. A particularly preferred blue dopant of this class is disclosed by Ricks et al.
In addition to singlet light-emitting dopants, triplet light-emitting dopants can also be useful in the present invention, particularly in green light-emitting layer 52g and yellow light-emitting layer 52y. Triplet light-emitting dopants useful in this invention have been described by Deaton et al. in U.S. patent application Ser. No. 11/749,883 and U.S. patent application Ser. No. 11/749,899, the contents of which are herein incorporated by reference.
Other OLED device layers that can be used in this invention have been well described in the art, and OLED devices 10 and 15, and other such devices described herein, can include layers commonly used for such devices. OLED devices are commonly formed on a substrate, e.g. OLED substrate 20. Such substrates have been well-described in the art. A bottom electrode is formed over OLED substrate 20 and is most commonly configured as an anode 30, although the practice of this invention is not limited to this configuration. When EL emission is viewed through the anode, the anode should be transparent, or substantially transparent, to the emission of interest. Common transparent anode materials used in the present invention are indium-tin oxide (ITO), indium-zinc oxide (IZO) and tin oxide, but other metal oxides can work including, but not limited to, aluminum- or indium-doped zinc oxide, magnesium-indium oxide, and nickel-tungsten oxide. In addition to these oxides, metal nitrides such as gallium nitride, and metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide, are used as the anode. For applications where EL emission is viewed only through the cathode electrode, the transmissive characteristics of the anode are immaterial and any conductive material can be used, regardless if it is transparent, opaque, or reflective. Example conductors for the present invention include, but are not limited to, gold, iridium, molybdenum, palladium, and platinum. Typical anode materials, transmissive or otherwise, have a work function no less than 4.0 eV. Desired anode materials can be deposited by any suitable process such as evaporation, sputtering, chemical vapor deposition, or electrochemical deposition. Anode materials can be patterned using well-known photolithographic processes.
Hole-transporting layer 40 can be formed and disposed over the anode. Other hole-transporting layers, e.g. 41 and 45, can be used with other light-emitting units, as described above. Desired hole-transporting materials can be deposited by any suitable process such as evaporation, sputtering, chemical vapor deposition, electrochemical deposition, thermal transfer, or laser thermal transfer from a donor material. Hole-transporting materials useful in hole-transporting layers include hole-transporting compounds described above as light-emitting hosts.
Electron-transporting layers, e.g. 55, 65, and 66, can contain one or more metal chelated oxinoid compounds, including chelates of oxine itself, also commonly referred to as 8-quinolinol or 8-hydroxyquinoline. Other electron-transporting materials include various butadiene derivatives as disclosed in U.S. Pat. No. 4,356,429 and various heterocyclic optical brighteners as described in U.S. Pat. No. 4,539,507. Benzazoles, oxadiazoles, triazoles, pyridinethiadiazoles, triazines, phenanthroline derivatives, and some silole derivatives are also useful electron-transporting materials.
An upper electrode most commonly configured as a cathode 90 is formed over the electron-transporting layer. If the device is top-emitting, the electrode must be transparent or nearly transparent. For such applications, metals must be thin (preferably less than 25 nm) or one must use transparent conductive oxides (e.g. indium-tin oxide, indium-zinc oxide), or a combination of these materials. Optically transparent cathodes have been described in more detail in U.S. Pat. No. 5,776,623. If the device is bottom-emitting, that is, where EL emission is viewed only through the anode electrode, the transmissive characteristics of the cathode are immaterial and any conductive material can be used. Cathode materials can be deposited by evaporation, sputtering, or chemical vapor deposition. When needed, patterning can be achieved through many well known methods including, but not limited to, through-mask deposition, integral shadow masking as described in U.S. Pat. No. 5,276,380 and EP 0 732 868, laser ablation, and selective chemical vapor deposition.
In OLED devices such as those described herein, one of the spaced electrodes is necessarily transmissive to visible light. The other electrode can be reflective. For example, in
OLED devices 10 and 15 can include other layers as well. For example, a hole-injecting layer 35 can be formed over the anode, as described in U.S. Pat. Nos. 4,720,432, 6,208,075, EP 0 891 121 A1, and EP 1 029 909 A1. An electron-injecting layer, such as alkaline or alkaline earth metals, alkali halide salts, or alkaline or alkaline earth metal doped organic layers, can also be present between the cathode and the electron-transporting layer.
The invention and its advantages can be better appreciated by the following comparative examples. Examples 2 to 4 are representative examples of this invention, while Example 1 is a non-inventive tandem OLED example for comparison purposes. The layers described as vacuum-deposited were deposited by evaporation from heated boats under a vacuum of approximately 10−6 Torr. After deposition of the OLED layers each device was then transferred to a dry box for encapsulation. The OLED has an emission area of 10 mm2. The devices were tested by applying a current of 20 mA/cm2 across electrodes. The results from Examples 1 to 4 are given in Table 1.
##STR00021##
##STR00022##
##STR00023##
##STR00024##
An OLED device was constructed as described above for Example 2 except that the hole-transporting layer thicknesses were varied as follows:
An OLED device was constructed as described above for Example 2 except that the hole-transporting layer thicknesses were varied as follows:
The results of these examples are shown in Table 1, below.
TABLE 1
Device data measured at 20 mA/cm2
Lum
Correlated
Efficiency
QE
Color
Device #
Voltage
(cd/A)
CIEx
CIEy
%
Temperature
Example 1
9.1
22.5
0.321
0.351
9.7
6,000 K
(Comparative)
Example 2
11.2
37.6
0.241
0.279
18.5
15,000 K
(Inventive)
Example 3
11.1
34.0
0.254
0.279
16.1
15,000 K
(Inventive)
Example 4
10.2
36.3
0.257
0.290
17.3
10,000 K
(Inventive)
Table 1 shows that higher color temperatures can be obtained with a display in accordance with this invention. The inventive examples show color temperatures in the desirable range of 9,000K to 13,000K. The inventive examples also show improved efficiency, with only a slight (1 to 2 volt) increase in driving voltage.
Examples 5 and 6 are some additional examples of this type of structure. The results for Examples 5 and 6 are given in Table 2.
##STR00025##
##STR00026##
An OLED device was constructed as described above for Example 5 except that the hole-transporting layer thicknesses were varied as follows:
The results of these examples are shown in Table 2, below.
TABLE 2
Device data measured at 1 mA/cm2
Lum
Correlated
Efficiency
QE
Color
Device #
Voltage
(cd/A)
CIEx
CIEy
%
Temperature
Example 5
9.7
72.8
0.345
0.368
27.9
5,000 K
(Comparative)
Example 6
9.6
72.1
0.360
0.380
26.9
4,600 K
(Comparative)
Examples 5 and 6 show OLED devices of the structure described herein that do not have emission with color temperature greater than 7,000K. Thus, it is necessary to also select the layers to have the desired color temperature for emission. It is conceivable that if higher-efficiency blue-emitting units are used in this embodiment of the invention, then color temperatures greater than 7,000K and high efficiency would be obtained.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
10 OLED device
15 OLED device
20 substrate
25r red color filter
25g green color filter
25b blue color filter
30 anode
31r anode
31g anode
31b anode
31w anode
35 hole-injecting layer
40 hole-transporting layer
41 hole-transporting layer
45 hole-transporting layer
50b blue light-emitting layer
51b blue light-emitting layer
52y yellow light-emitting layer
52g green light-emitting layer
55 electron-transporting layer
65 electron-transporting layer
66 electron-transporting layer
75 light-emitting unit
80 light-emitting unit
85 light-emitting unit
90 cathode
95 intermediate connector
96 intermediate connector
110 curve
120 curve
130 curve
140 curve
Spindler, Jeffrey P., Hatwar, Tukaram K.
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| Mar 04 2010 | Eastman Kodak Company | Global Oled Technology LLC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 024068 | /0468 |
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